EP4205990A1 - Matériau d'enregistrement thermosensible - Google Patents

Matériau d'enregistrement thermosensible Download PDF

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Publication number
EP4205990A1
EP4205990A1 EP21861708.2A EP21861708A EP4205990A1 EP 4205990 A1 EP4205990 A1 EP 4205990A1 EP 21861708 A EP21861708 A EP 21861708A EP 4205990 A1 EP4205990 A1 EP 4205990A1
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EP
European Patent Office
Prior art keywords
amino
group
thermosensitive recording
amino group
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP21861708.2A
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German (de)
English (en)
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EP4205990A4 (fr
Inventor
Kousuke SHIBAGAKI
Yousuke TODA
Hidehiro Arai
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Publication of EP4205990A1 publication Critical patent/EP4205990A1/fr
Publication of EP4205990A4 publication Critical patent/EP4205990A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
    • B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • B41M5/3275—Fluoran compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337—Additives; Binders
    • B41M5/3375—Non-macromolecular compounds

Definitions

  • the present invention relates to a thermosensitive recording material utilizing coloring by a reaction between a color forming dye and a color developing agent.
  • thermosensitive recording material is obtained by separately dispersing a leuco dye and a color developing agent such as a phenolic compound in a form of fine particles, then mixing the dispersed leuco dye and the dispersed color developing agent, and adding an additive such as a binder, a sensitizer, a filler, or a lubricant to the mixture to obtain a coating liquid; and then applying the coating liquid to paper, a film, synthetic paper, or the like.
  • the thermosensitive recording material produces a color through a chemical reaction that occurs by melting one or both of the leuco dye and the color developing agent by heating to bring the leuco dye and the color developing agent into contact with each other.
  • thermosensitive recording material To induce the color formation of such a thermosensitive recording material, a thermal printer equipped with a thermal head or the like is used.
  • this thermosensitive recording method has such characteristics that (1) no noise is generated at the time of recording, (2) there is no requirement for developing or fixing an image, (3) free from maintenance, and (4) a machine is relatively inexpensiveness; and has been therefore widely used in the fields of a facsimile, output of a computer, a printer of a calculator or the like, a recorder of a medical instrument, an automatic ticket vending machine, a thermosensitive recording label, and the like.
  • thermosensitive recording material In recent years, as applications of a thermosensitive recording material has expanded, a need for high-speed recording has been increasing. Specifically, there is a strong need for development of a thermosensitive recording material having excellent thermal responsiveness and sufficiently adaptable to high-speed recording. In order to satisfy such a need, research and development of a color forming dye, a color developing agent, a stabilizer, and the like have been performed, but those that sufficiently balance color sensitivity, image stability, and the like have not been found yet.
  • a color developing compound having a phenolic hydroxy group has high color developing capability.
  • many reports for bisphenol-based compounds have been made due to high intensity thereof, and 2,2-bis(4-hydroxyphenylpropane) (bisphenol A) (Patent Literature 1), 4,4'-dihydroxydiphenylsulfone (bisphenol S) (Patent Literature 2), and the like have been proposed.
  • bisphenol A 2,2-bis(4-hydroxyphenylpropane)
  • bisphenol S bisphenol S
  • Patent Literature 2 2,4'-dihydroxydiphenylsulfone
  • these compounds have high melting points, and therefore are inferior in thermal responsiveness, and also have disadvantages that printed portions are inferior in water resistance and a background is inferior in heat resistance.
  • thermosensitive recording material containing a specific color developing compound which provides printed portions having excellent water resistance and a background exhibiting high stability to heat (Patent Literature 3), but that material is insufficient in terms of plasticizer resistance of the printed portions.
  • a cross-linked diphenylsulfone compound (Patent Literature 4) and a urea urethane compound (Patent Literature 5) have been proposed as color developing compounds providing high stability to a plasticizer, but they have a problem of low thermal responsiveness.
  • thermosensitive recording material containing a specific color developing compound and a urea urethane compound in combination which provides printed portions with improved stability.
  • the combined urea urethane compound causes significant background fogging when the thermosensitive recording material is stored in a high humidity environment. Therefore, there is a need for a thermosensitive recording material which not only achieves high thermal responsiveness but also provide printed portions and a background with good stability.
  • An object of the present invention is to provide a recording material and a recording sheet containing, as a color developing agent, a non-phenolic compound wherein a printed portion exhibits excellent water resistance and a background portion exhibits favorable heat resistance as compared with the prior art.
  • thermosensitive recording material containing a compound represented by the following general formula (1) as a color developing compound provides printed portions having excellent water resistance and a background portion having excellent heat resistance and thus completed the present invention.
  • the present invention relates to:
  • the present invention provides a thermosensitive recording material which provides printed portions with excellent coloring property and water resistance, and a background with excellent heat resistance.
  • the present invention relates to a thermosensitive recording material containing a compound represented by general formula (1) as a color developing compound, and a thermosensitive recording layer and a thermosensitive recording paper containing the thermosensitive recording material.
  • examples of the halogen atom in R 1 to R 10 of general formula (1) include a fluorine atom, a chlorine atom, and a bromine atom, and a fluorine atom or a chlorine atom is preferable.
  • examples of the alkyl group in R 1 to R 10 of general formula (1) include a linear, branched or cyclic alkyl group, and among them a linear or branched alkyl group is preferable, and a linear alkyl group is more preferable.
  • the number of carbon atoms is usually in the range of C1 to C12, preferably C1 to C8, more preferably C1 to C6, and still more preferably C1 to C4.
  • a linear alkyl group such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl; a branched alkyl group such as isopropyl, isobutyl, sec-butyl, t-butyl, isopentyl, isohexyl, and isooctyl; and a cyclic alkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • a linear alkyl group such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n
  • examples of the alkoxy group in R 1 to R 10 of general formula (1) include a linear, branched or cyclic alkoxy group, and among them a linear or branched alkoxy group is preferable, and a linear alkoxy group is more preferable.
  • the number of carbon atoms is usually in the range of C1 to C12, preferably C1 to C8, more preferably C1 to C6, and still more preferably C1 to C4.
  • a linear alkoxy group such as methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexyloxy, n-heptoxy, n-octyloxy, n-nonyloxy, and n-decyloxy; a branched (preferably C3 to C10) alkoxy group such as isopropoxy, isobutoxy, sec-butoxy, t-butoxy, isoamyloxy, t-amyloxy, isohexyloxy, t-hexyloxy, isoheptoxy, t-heptoxy, isooctyloxy, t-octyloxy, 2-ethylhexyloxy, isononyloxy, and isodecyloxy; and a cyclic (preferably C3 to C7) alkoxy group such as cyclopropoxy, cyclobutoxy, cyclopentoxy,
  • the aryl oxy group in R 1 to R 10 of general formula (1) is preferably a C6 to C12 aryl oxy group, and specific examples thereof include phenoxy, naphthyloxy, and biphenyloxy.
  • examples of the alkyl carbonyl oxy group in R 1 to R 10 of general formula (1) include a linear, branched or cyclic alkyl carbonyl oxy group. Among them, a C1 to C10 alkyl carbonyl oxy group is preferable.
  • a linear alkyl carbonyl oxy group such as methyl carbonyl oxy, ethyl carbonyl oxy, n-propyl carbonyl oxy, n-butyl carbonyl oxy, n-pentyl carbonyl oxy, n-hexyl carbonyl oxy, n-heptyl carbonyl oxy, n-octyl carbonyl oxy, n-nonyl carbonyl oxy, and n-decyl carbonyl oxy; a branched (preferably C3 to C10) carbonyl oxy group such as isopropyl carbonyl oxy, isobutyl carbonyl oxy, sec-butyl carbonyl oxy, t-butyl carbonyl oxy, isoamyl carbonyl oxy, t-amyl carbonyl oxy, isohexyl carbonyl oxy, t-hexyl carbonyl oxy,
  • the aryl carbonyl oxy group in R 1 to R 10 of general formula (1) is preferably a C6 to C12 aryl carbonyl oxy group, and specific examples thereof include phenyl carbonyl oxy, naphthyl carbonyl oxy, and biphenyl carbonyl oxy.
  • examples of the alkyl carbonyl amino group in R 1 to R 10 of general formula (1) include a linear, branched or cyclic alkyl carbonyl amino group. Among them, a C1 to C10 alkyl carbonyl amino group is preferable.
  • a linear alkyl carbonyl amino group such as methyl carbonyl amino, ethyl carbonyl amino, n-propyl carbonyl amino, n-butyl carbonyl amino, n-pentyl carbonyl amino, n-hexyl carbonyl amino, n-heptyl carbonyl amino, n-octyl carbonyl amino, n-nonyl carbonyl amino, and n-decyl carbonyl amino; a branched (preferably C3 to C10) carbonyl amino group such as isopropyl carbonyl amino, isobutyl carbonyl amino, sec-butyl carbonyl amino, t-butyl carbonyl amino, isoamyl carbonyl amino, t-amyl carbonyl amino, isohexyl carbonyl amino, t-hexyl carbonyl amino, isoheptyl carbonyl amino, t-heptyl carbony
  • the aryl carbonyl amino group in R 1 to R 10 of general formula (1) is preferably a C6 to C12 aryl carbonyl amino group. Specific examples thereof include phenyl carbonyl amino, naphthyl carbonyl amino, and biphenyl carbonyl amino.
  • examples of the alkyl sulfonyl amino group in R 1 to R 10 of general formula (1) include a linear, branched or cyclic alkyl sulfonyl amino group. Among them, a C1 to C10 alkyl sulfonyl amino group is preferable.
  • a linear alkyl sulfonyl amino group such as methyl sulfonyl amino, ethyl sulfonyl amino, n-propyl sulfonyl amino, n-butyl sulfonyl amino, n-pentyl sulfonyl amino, n-hexyl sulfonyl amino, n-heptyl sulfonyl amino, n-octyl sulfonyl amino, n-nonyl sulfonyl amino, and n-decyl sulfonyl amino; a branched (preferably C3 to C10) sulfonyl amino group such as isopropyl sulfonyl amino, isobutyl sulfonyl amino, sec-butyl sulfonyl amino, t-butyl sulfonyl amino,
  • the aryl sulfonyl amino group in R 1 to R 10 of general formula (1) is preferably a C6 to C12 aryl sulfonyl amino group. Specific examples thereof include phenyl sulfonyl amino, toluene sulfonyl amino, naphthyl sulfonyl amino, and biphenyl sulfonyl amino.
  • examples of the monoalkyl amino group in R 1 to R 10 of formula (1) include a linear, branched or cyclic monoalkyl amino group. Among them, a mono C1 to C10 alkyl amino group is preferable.
  • a linear monoalkyl amino group such as methyl amino, ethyl amino, n-propyl amino, n-butyl amino, n-pentyl amino, n-hexyl amino, n-heptyl amino, n-octyl amino, n-nonyl amino, and n-decyl amino; a branched (preferably C3 to C10) monoalkyl amino group such as isopropyl amino, isobutyl amino, sec-butyl amino, t-butyl amino, isoamyl amino, t-amyl amino, isohexyl amino, t-hexyl amino, isoheptyl amino, t-heptyl amino, isooctyl amino, t-octyl amino, 2-ethylhexyl amino, isononyl amino, and isodecyl amino; and a cyclic (preferably C3 to C
  • examples of the dialkyl amino group in R 1 to R 10 of general formula (1) include a linear, branched or cyclic dialkyl amino group. Among them, a di C1 to C10 alkyl amino group is preferable.
  • a linear dialkyl amino group such as dimethyl amino, diethyl amino, di-n-propyl amino, di-n-butyl amino, di-n-pentyl amino, di-n-hexyl amino, di-n-heptyl amino, di-n-octyl amino, di-n-nonyl amino, and di-n-decyl amino; a branched dialkyl amino group (preferably having two C3 to C10 branched chains) such as diisopropyl amino, diisobutyl amino, di-sec-butyl amino, di-t-butyl amino, diisoamyl amino, di-t-amyl amino, diisohexyl amino, di-t-hexyl amino, diisoheptyl amino, di-t-heptyl amino, diisooctyl amino, di-t-octyl amino, di-(2-ethylhexyl) amino
  • examples of the aryl amino group in R 1 to R 10 of general formula (1) include a monoaryl amino group and a diaryl amino group. Among them, a mono C6 to C12 aryl amino group is preferable. Specific examples thereof include phenylamino (anilino), naphthylamino, and biphenylamino. Examples of the aryl amino group also include a di C6 to C12 aryl amino group. Specific examples thereof include diphenylamino, dinaphthylamino, and di(biphenyl) amino.
  • the compound represented by general formula (1) is preferably a compound represented by general formula (2).
  • R 1 to R 3 in the general formula (2) each preferably represent an alkyl group or a hydrogen atom, more preferably represent a linear C1 to C4 alkyl group or a hydrogen atom, and particularly preferably represent a methyl group or a hydrogen atom.
  • the substitution position of a substituent represented by general formula (3) may be an ortho position, a meta position, and a para position, and a para position or a meta position is preferable.
  • the compounds of general formula (1) can be obtained, for example, by a known synthesis method as described in European Journal of Medicinal Chemistry (2017), 125, 865-880 (Non-Patent Literature 1).
  • R 1 to R 10 are the same as defined above.
  • the compounds of general formula [1-2] can be manufactured by causing the compound of general formula [1-1] to react with a phenyl isocyanate compound in the presence or absence of a base.
  • a solvent used in this reaction is not particularly limited as long as the solvent does not affect the reaction, and examples thereof include: an amide compound such as N,N-dimethylformamide, N,N-dimethylacetamide, or N-methylpyrrolidone; a halogenated hydrocarbon compound such as methylene chloride or chloroform; an aromatic hydrocarbon compound such as benzene, toluene, or xylene; an ether compound such as dioxane, tetrahydrofuran, anisole, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, or diethylene glycol diethyl ether; a nitrile compound such as acetonitrile; a ketone compound such as acetone or 2-butanone; an
  • the amount of a phenyl isocyanate compound used in this reaction is usually 0.1 to 50 fold mol, and preferably 0.5 to 3 fold mol with respect to that of the compound of general formula [1-1].
  • Examples of the base optionally used in this reaction include: an inorganic base such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium hydrogen carbonate, potassium carbonate, and cesium carbonate; and an organic base such as triethylamine, and diisopropylethylamine.
  • the amount of a base used in the reaction is usually 0.1 to 50 fold mol, and preferably 0.5 to 5 fold mol with respect to that of the compound of general formula [1-1].
  • a reaction temperature of this reaction is usually -78 to 120°C, and preferably -10 to 80°C.
  • the reaction may be performed for 10 minutes to 24 hours.
  • the compounds of general formula [1-3] can be manufactured by causing a compound of general formula [1-2] to react with phosphorus oxychloride, thionyl chloride, chlorosulfonic acid, oxalyl chloride, or the like in the presence or absence of a base to form a chloride sulfonate, and subsequently the chloride sulfonate is caused to react with a phenol compound, or caused to react with a phenol compound through direct dehydration condensation.
  • a solvent used in this reaction is not particularly limited as long as the solvent does not affect the reaction, and examples thereof include: an amide compound such as N,N-dimethylformamide, N,N-dimethylacetamide, or N-methylpyrrolidone; a halogenated hydrocarbon compound such as methylene chloride or chloroform; an aromatic hydrocarbon compound such as benzene, toluene, or xylene; an ether compound such as dioxane, tetrahydrofuran, anisole, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, or diethylene glycol diethyl ether; a nitrile compound such as acetonitrile; a ketone compound such as acetone or 2-butanone; an ester compound such as ethyl acetate or butyl acetate; a sulfone compound such as sulfolane; a sulfoxide compound such as di
  • the amount of the phenol compound used in this reaction is 0.1 to 50 fold mol, and preferably 0.7 to 3 fold mol with respect to that of the compound of general formula [1-2].
  • a reaction temperature is usually -78 to 100°C, and preferably -20 to 80°C. The reaction may be performed for 10 minutes to 24 hours.
  • thermosensitive recording material In forming a thermosensitive recording material, a color-forming compound is usually used in an amount of 1 to 50% by mass, preferably 5 to 30% by mass; and a compound represented by general formula (1) is usually used in an amount of 1 to 70% by mass, and preferably 10 to 50% by mass.
  • a sensitizer is usually used in an amount of 1 to 80% by mass; a stabilizer is usually used in an amount of 0 to 30% by mass; a binder is usually used in an amount of 1 to 90% by mass; a filler is usually used in an amount of 0 to 80% by mass; and each of other components such as a lubricant, a surfactant, a defoamer, and an ultraviolet absorber may be used at any ratio and is usually used, for example, in an amount of 0 to 30% by mass.
  • % by mass indicates a mass ratio of each component in a thermosensitive recording layer.
  • a compound represented by formula (1) is usually used in a mass ratio range of 0.5 to 20 times, more preferably in a mass ratio range of 1 to 5 times with respect to a color-forming compound.
  • a thermosensitive recording material of the present invention may comprise another color developing compound, a sensitizer, or other additives known in the art other than the above components.
  • the color-forming compound is not particularly limited and may be a compound ordinarily used for a pressure-sensitive recording paper or a thermosensitive recording paper.
  • the color-forming compound include a fluoran-based compound, a triarylmethane-based compound, a spiro-based compound, a diphenylmethane-based compound, a thiazine-based compound, a lactam-based compound, and a fluorene-based compound; and a fluoran-based compound is preferable.
  • fluoran-based compound examples include 3-diethylamino-6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3-(N-methyl-N-cyclohexylamino)-6-methyl-7-anilinofluoran, 3-(N-ethyl-N-isopentylamino)-6-methyl-7-anilinofluoran, 3-(N-ethyl-N-isobutylamino)-6-methyl-7-anilinofluoran, 3-[N-ethyl-N-(3-ethoxypropyl) amino]-6-methyl-7-anilinofluoran, 3-(N-ethyl-N-hexylamino)-6-methyl-7-anilinofluoran, 3-dipentylamino-6-methyl-7-anilinofluoran, 3-(N-methyl-N-propylamino)-6-methyl-7-anilin
  • triarylmethane-based compound examples include 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (another name: crystal violet lactone or CVL), 3,3-bis(p-dimethylaminophenyl) phthalide, 3-(p-dimethylaminophenyl)-3-(1,2-dimethylaminoindol-3-yl) phthalide, 3-(p-dimethylaminophenyl)-3-(2-methylindol-3-yl) phthalide, 3-(p-dimethylaminophenyl)-3-(2-phenylindol-3-yl) phthalide, 3,3-bis(1,2-dimethylindol-3-yl)-5-dimethylaminophthalide, 3,3-bis(1,2-dimethylindol-3-yl)-6-dimethylaminophthalide, 3,3-bis(9-ethylcarbazol-3-yl)-5
  • spiro-based compound examples include 3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran, 3,3'-dichlorospirodinaphthopyran, 3-benzylspirodinaphthopyran, 3-propylspirobenzopyran, 3-methylnaphtho-(3-methoxybenzo) spiropyran, and 1,3,3-trimethyl-6-nitro-8'-methoxyspiro (indoline-2,2'-benzopyran).
  • diphenylmethane-based compound examples include N-halophenyl-leucoauramine, 4,4-bis-dimethylaminophenylbenzhydryl benzyl ether, and N-2,4,5-trichlorophenyl leucoauramine.
  • thiazine-based compound examples include benzoyl leucomethylene blue and p-nitrobenzoyl leucomethylene blue.
  • lactam-based compound include rhodamine B anilinolactam and rhodamine B-p-chloroanilinolactam.
  • fluorene-based compound examples include 3,6-bis(dimethylamino) fluorene spiro (9,3')-6'-dimethylaminophthalide, 3,6-bis(dimethylamino) fluorene spiro (9,3')-6'-pyrrolidinophthalide, and 3-dimethylamino-6-diethylaminofluorene spiro (9,3')-6'-pyrrolidinophthalide.
  • color-forming compounds are used singly or in combination thereof.
  • Another color developing compound that can be used in combination with those of the present invention are not particularly limited and may be a compound ordinarily used for a pressure-sensitive recording paper or a thermosensitive recording paper, and examples thereof include: a phenolic compound such as ⁇ -naphthol, ⁇ -naphthol, p-octylphenol, 4-t-octylphenol, p-t-butylphenol, p-phenylphenol, 1,1-bis(p-hydroxyphenyl) propane, 2,2-bis(p-hydroxyphenyl) propane (also referred to as bisphenol A or BPA), 2,2-bis(p-hydroxyphenyl) butane, 1,1-bis(p-hydroxyphenyl) cyclohexane, 4,4'-thiobisphenol, 4,4'-cyclo-hexylidenediphenol, 2,2'-bis(2,5-dibrom-4-hydroxyphenyl) propane, 4,4'-isopropylidenebis(2-t-but
  • the sensitizer thermal fusible compound
  • a wax such as an animal or vegetable wax or a synthetic wax
  • a higher fatty acid such as an animal or vegetable wax or a synthetic wax
  • a higher fatty acid such as an animal or vegetable wax or a synthetic wax
  • a higher fatty acid such as an animal or vegetable wax or a synthetic wax
  • a higher fatty acid such as an animal or vegetable wax or a synthetic wax
  • a higher fatty acid such as an animal or vegetable wax or
  • the wax include a vegetable wax, a carnauba wax, shellac, paraffin, a montan wax, oxidized paraffin, a polyethylene wax, and oxidized polyethylene.
  • the higher fatty acid include stearic acid and behenic acid.
  • the higher fatty acid amide include stearic acid amide, oleic acid amide, N-methyl stearic acid amide, erucic acid amide, methylol behenic acid amide, methylene bis stearic acid amide, and ethylene bis stearic acid amide.
  • the higher fatty acid anilide include stearic acid anilide and linoleic acid anilide.
  • naphthalene derivative examples include 1-benzyloxynaphthalene, 2-benzyloxynaphthalene, phenyl 1-hydroxy naphthoate, and 2,6-diisopropylnaphthalene.
  • aromatic ether examples include 1,2-diphenoxyethane, 1,4-diphenoxybutane, 1,2-bis(3-methylphenoxy) ethane, 1,2-bis(4-methoxyphenoxy) ethane, 1,2-bis(3,4-dimethylphenyl) ethane, 1-phenoxy-2-(4-chlorophenoxy) ethane, 1-phenoxy-2-(4-methoxyphenoxy) ethane, 1,2-diphenoxymethylbenzene, and diphenyl glycol.
  • aromatic carboxylic acid derivative examples include benzyl p-hydroxybenzoate, benzyl p-benzyloxybenzoate, and dibenzyl terephthalate.
  • aromatic sulfonic acid ester derivative examples include phenyl p-toluenesulfonate, phenyl mesitylenesulfonate, 4-methylphenyl mesitylenesulfonate, and 4-tolyl mesitylenesulfonate.
  • carbonic acid or oxalic acid diester derivative examples include diphenyl carbonate, dibenzyl oxalate, di(4-chlorobenzyl) oxalate, and di(4-methylbenzyl) oxalate.
  • Examples of the biphenyl derivative include p-benzylbiphenyl and p-allyloxybiphenyl.
  • Examples of the terphenyl derivative include m-terphenyl.
  • Examples of the sulfone derivative include p-toluene sulfonamide, benzene sulfonanilide, p-toluene sulfonanilide, 4,4'-diallyloxy diphenyl sulfone, and diphenyl sulfone.
  • Examples of the aromatic ketone derivative include 4,4'-dimethyl benzophenone and dibenzoyl methane.
  • Examples of the aromatic hydrocarbon compound include p-acetotoluidine.
  • the stabilizer include: a hindered phenol compound such as 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylidenebis(4-ethyl-6-t-butylphenol), 2,2'-ethylidenebis(4,6-di-t-butylphenol), 4,4'-thiobis(2-methyl-6-t-butylphenol), 4,4'-butylidenebis(6-t-butyl-m-cresol), 1-[ ⁇ -methyl- ⁇ -(4'-hydroxyphenyl) ethyl]-4-[ ⁇ ', ⁇ '-bis(4'-hydroxyphenyl) ethyl] benzene, 1,1,3-tris(2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) butane, tris(2,6-dimethyl-4-t-butyl
  • the binder include: a water-soluble polymer such as methyl cellulose, methoxy cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, cellulose, polyvinyl alcohol (PVA), carboxyl group-modified polyvinyl alcohol, sulfonic acid group-modified polyvinyl alcohol, silyl group-modified polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polyacrylic acid, starch and a derivative thereof, casein, gelatin, a water-soluble isoprene rubber, an alkali salt of a styrene/maleic anhydride copolymer, and an alkali salt of an iso (or diiso) butylene/maleic anhydride copolymer; and a hydrophobic polymer such as a (meth)acrylate copolymer, a styrene/(meth)acrylate copolymer, polyurethane, a
  • the filler examples include calcium carbonate, magnesium carbonate, magnesium oxide, silica, white carbon, talc, clay, alumina, magnesium hydroxide, aluminum hydroxide, aluminum oxide, barium sulfate, a polystyrene resin, and a urea-formalin resin.
  • Example of the additive include: a metal salt of a higher fatty acid such as zinc stearate or calcium stearate, which can be used for preventing the abrasion of thermal heads, or preventing sticking; an ultraviolet absorber such as a phenol derivative, a benzophenone-based compound, and a benzotriazole-based compound, which can be used for imparting an antioxidative or antiaging effect; various surfactants; and a defoaming agent.
  • a metal salt of a higher fatty acid such as zinc stearate or calcium stearate, which can be used for preventing the abrasion of thermal heads, or preventing sticking
  • an ultraviolet absorber such as a phenol derivative, a benzophenone-based compound, and a benzotriazole-based compound, which can be used for imparting an antioxidative or antiaging effect
  • various surfactants such as sodium stearate, sodium stearate, sodium stearate, sodium stearate, sodium stearate, sodium
  • thermosensitive recording material and a thermosensitive recording sheet are separately pulverized and dispersed, if necessary, with a binder or other additives by a dispersing machine such as a ball mill, an attritor, or a sand mill to prepare dispersions (usually water is used as a medium when pulverization or dispersion is performed in a wet manner).
  • a dispersing machine such as a ball mill, an attritor, or a sand mill to prepare dispersions (usually water is used as a medium when pulverization or dispersion is performed in a wet manner).
  • the dispersions are then mixed to prepare a coating liquid, and the coating liquid is applied onto a support such as paper (plain paper, high quality paper, coated paper, or the like can be used), a plastic sheet, or synthetic paper in such an amount as to usually provide a dry mass of 1 to 20 g/m 2 with a bar coater, a blade coater or the like, and dried to form a thermosensitive recording layer and thus a thermosensitive recording sheet.
  • a support such as paper (plain paper, high quality paper, coated paper, or the like can be used), a plastic sheet, or synthetic paper in such an amount as to usually provide a dry mass of 1 to 20 g/m 2 with a bar coater, a blade coater or the like, and dried to form a thermosensitive recording layer and thus a thermosensitive recording sheet.
  • an intermediate layer may be disposed between the thermosensitive recording layer and the support, or an overcoat layer (protective layer) may be disposed on the thermosensitive recording layer.
  • the intermediate layer and the overcoat layer (protective layer) can be formed, for example, by pulverizing and dispersing the binder, if necessary, together with other additives in a similar manner to the preparation of a coating liquid for the thermosensitive recording material to prepare a coating liquid for the intermediate layer or a coating liquid for the overcoat layer (protective layer), then applying the coating liquid in such an amount as to usually provide a dry mass of 0.1 to 10 g/m 2 , and then drying the coating liquid.
  • Liquid [B] containing a color-forming compound.
  • Liquid [B] 3-Dibutylamino-6-methyl-7-anilinofluoran 35 parts 15% PVA aqueous solution 40 parts Water 25 parts
  • thermosensitive recording material coating liquid was applied at a dry mass of 5 g/m 2 onto high quality paper having a basis weight of 50 g/m 2 and dried to form a thermosensitive recording layer.
  • a protective layer coating liquid having the following composition was applied at a dry mass of 2 g/m 2 onto the above thermosensitive recording layer and dried to prepare a thermosensitive recording paper with a protective layer.
  • [Table 5] 40% Styrene/acrylate ester copolymer emulsion 115 parts 5% Bentonite aqueous dispersion 17 parts 45% Styrene/acrylic copolymer aqueous emulsion 44 parts 39% Zinc stearate aqueous dispersion 103 parts 67% Calcium carbonate aqueous dispersion 15 parts
  • thermosensitive recording paper with a protective layer was obtained in a similar manner to Example 1 except that a mixture having the following composition was pulverized and dispersed with a Sandoz grinder such that a median particle diameter was 1 ⁇ m, which was obtained by a laser diffraction/scattering particle size distribution measuring apparatus LA-950 (Horiba, Ltd.), to prepare Liquid [C], and Liquid [C] was used in place of Liquid [A] in the composition of the thermosensitive recording layer coating liquid described in Example 1 above and the components were mixed at the following composition to prepare a thermosensitive recording material coating liquid.
  • Liquid [C] Bisphenol S (Tokyo Chemical Industry Co., Ltd.) 25 parts 25% PVA aqueous solution 20 parts Water 55 parts
  • thermosensitive recording papers obtained in Example 1 and Comparative Example 1 were printed at a pulse width of 1.2 msec using a thermal printer (TH-M2/PP) manufactured by Okura Engineering Co., Ltd., and were then immersed in water at 25°C for 24 hours.
  • the Macbeth reflection density of a colored portion of each of the papers before and after the test was measured using a colorimeter manufactured by GRETAG-MACBETH, trade name "SpectroEye”.
  • the measurements were performed under the conditions of using Illuminant C as a light source, ANSI A as a density reference, and a viewing angle of 2 degrees.
  • the results are shown in Table 7 below. It is to be noted that the higher a residual ratio is, the better water resistance is.
  • Residual ratio % Macbeth reflection density of colored portion after test / Macbeth reflection density of colored portion before test ⁇ 100 [Table 7] Water resistance test Example 1 Comparative Example 1 Residual ratio (%) 100 76
  • Example 1 in which a compound of the present invention was used as a color developing compound has a higher residual ratio than Comparative Example 1, in which bisphenol S described in Patent Literature 2 was used as a color developing compound, which evidences that the present invention is more excellent in water resistance of colored portions than the prior art.
  • thermosensitive recording papers obtained in Example 1 and Comparative Example 1 were held at 90°C for one hour in an air blowing constant temperature thermostat manufactured by Yamato Scientific Co., Ltd., trade name: DKN 402.
  • ISO brightness degrees of a background before and after the test were measured using a colorimeter manufactured by GRETAG-MACBETH, trade name "SpectroEye". The measurements were performed under the conditions of using Illuminant C as a light source, ANSI A as a density reference, and a viewing angle of 2 degrees. Results are shown in Table 3 below. It is to be noted that the smaller an amount of change in the ISO brightness between before and after the test is, the better heat resistance of a background is. [Table 8] Heat resistance test Example 1 Comparative Example 1 Background Before test 82. 9 76. 7 After test 77. 1 64. 4 Amount of change 5. 8 12. 3
  • Example 1 using the color developing compound of the present invention has a small amount of change in the ISO whiteness before and after the heat resistance test. Therefore, it is found that Example 1 is superior in the heat resistance of the background to Comparative Example 1 using bisphenol S that is s a color developing compound described in Patent Literature 2.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
EP21861708.2A 2020-08-27 2021-08-27 Matériau d'enregistrement thermosensible Withdrawn EP4205990A4 (fr)

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